Composition comprising a phenolic resin and process of making same



UNITED STATES PATENT OFFICE 2,087,853 COMPOSITION COMPRISING A PHENOLICRESIN AND PROCESS OF MAKING SADIE Carleton Ellis, Montclair, N. J.,as'signor to Ellis- Foster Company, a corporation of New Jersey NoDrawing.

4 Claims.

In Serial 751,867 flied Nov. 24, 1924, and related applications, such asSerial 578,219 flied Nov. 30, 1931, I have disclosed methods of makingresins by reaction between aldehydes and xylenols or coal tar fractionscontaining an influential proportion of xylenols.

One utilization of these xylenitic resins is in the production ofvarnishes by incorporation with drying oils. Thus The oil-soluble actingxylenol and Example 1.61

Serial 578,219 states: resin may be made by reacetaldehyde as follows:

parts by weight xylenol fraction boiling point 205- 212 C.

parts paraldehyde part orthophosphoric acid The phosphoric acid wasadded to the xylenol and the mixture heated to about 45 0., and theparaldehyde introduced very period of /2 hour. immediately aftergradually -over a The heat was cut off almost beginning to introduce theparaldehyde and the temperature rose spontaneously to about C. Theproduct was washed to remove the free phosphoric acid and dried. Oncooling avbrownish, hard resin was obtained. 1 part of this resin wasfound to dissolve readily in, for example, 4 perature of about uble intung oil.

parts of linseed oil at a tem- C. The resin also is sol- Thinners suchas turpentine,

and the like, may be added, also driers as required.

In view of the te duction of the resin some ing on the large mperatureincrease in the proprovision when workscale for cooling the reactionproduct in the making should be applied in most cases.

Acetaldehyde likewise re cts with certain xylenol derivatives to giveoil-soluble resins (by the term oil-soluble" from the standpoint of thepresent invention the glyceride oils such as the drying and semi-dryingoils, and the like,

are intended).

976 parts by weight of crude xy-' were heated under dimethylmethane. To100 parts of Example 2.-232 parts by weight acetone 5 parts by weightconcentrated hydrochloric acid lenol, bofling range 205- 225 C.

a reflux condenser for- 12 hours The reaction was dihydroxydixylylsaidheavy viscous oil without In this way a composite resin hydeformaldehyde type dissolved in the linseed Application November 4, 1932,Serial No. 641,232

temperature being carried to -100 0. The reaction product was washed anddried resulting in obtaining a soft resin which was almost completelysoluble inhot linseed or tung oil or mixtures of these.

In coating compositions of the varnish type made from xylenolacetaldehyde resin, an oil of the linseed and tung 011 type, a drier anda thinner, I may secure a resinous component of a somewhat highermelting point by reacting on the xylenol acetaldehyde resin in solutionin a drying oil by a reagent such as formaldehyde orhexamethylenetetramlne, heating the composition until the desired degreeof hardness occurs without sacrifice of solubility of the product.

of the acetaldeoil, tung oil, and the like, with suitable thinners, suchas turpentine, is obtained which tends to give harder coatings on dryingthan those which have not received the formaldehyde hardening treatment.In like manner coating compositions may be made without the addition ofhexamethylenetetramine, paraform, and so forth, then the hardening agentadded and the coating applied and baked at a reactive temperature tocause hardening to set in in the coating,.to convert the resin'to thedesired degree.

In Serial 383,167, filed Aug. considers among other matters theemployment of mixed aldehydes obtained for example by the oxidationtreatment of natural gas and the like, I have noted the step ofremovalfrom the resin of ,unreacted components and bodies of unpleasantodor as follows:

I preferably blow with air or steam or inert gas at a temperature above,C. to de-acridify. At the same time I am able to remove excess ofxylenol or other phenolic body and this frequent- 2, 1929, which ly isdesirable, especially whenv a resin is being made for use the presenceof free phenolic to retard drying.

-Whenthe de-acridiflcation step is complete the resin may be made into amolding composition -by incorporating with the various fillers used in:the plastic industry and with the addition of hexamethylenetetramine orother hardening agent and hot pressed. Or the clear resin, withorwithout some added hardening agent, may be slowly baked over a longperiod to form various amber substitutes, and the like, which may bemachined to form cigarette holders, beads, um-

brella handles, and so forth. Or a solution may be made from the resinby dissolving it in a solvent mixture such as alcohol-benzol and thelatter employed for impregnation, for example, of paper or cloth and thedried impregnated sheets hot pressed to form laminated sheet, fiberboard, gear blanks, and the like. Or the resin may be heated with rosinto a temperature between 200-300 C. using an excess of rosin and finallyesterifying with glycerol, glycol, diethylene glycol, and the like, toform oil soluble resins which may be used in making varnishes.

Acetaldehyde forms with phenolic bodies a resin having somewhatdifferent properties from that obtained by the use of formaldehyde. Byreacting on a phenol with a mixture of formaldehyde and acetaldehyde acomplex is secured which is eminently desirable. Using the crude mixedaldehydes from natural'gas oxidation containing a major proportion offormaldehyde and a minor proportion of acetaldehyde I am able to secureco-reacted products or complexes relatively low in cost and havingproperties substantially those of resins made from raw materials costingconsiderably more.

The present invention is based in part at least on such disclosures andis further illustrated by the following examples:

Example 3.2000 parts by weight of xylenol distillate with boiling rangefrom 210-225 C.

was heated with 1000 parts of 37% aqueous formaldehyde solution in avessel provided with a reflux condenser. Water was then boiled off andthe temperature raised to 110 C. A soft resin of strong phenolic odorwas obtained. This soft resin was heated to 160 C. and blown with steamat approximately this temperature for 3 hours. When cold the resultingresin was hard, light in color and dissolved in hot tung oil. It waswell de-acridified, being practically free of odor.

From 500 parts of the soft resin the steamblowing or steam-distillationyielded 107 parts of an oily liquid heavier than water. This oily liquidwas separated from the aqueous portion of the distillate and fromvarious tests appeared to consist in large measure of 1,3,4-xylenol.

Example 4.Instead of steam-stilling thesoft resin of Example 3, 1000parts were heated to 230 C. and held at this temperature for about 5minutes. On cooling, the resin was hard, possessed about the same coloras the steamstilled hard resin of Example 3, and dissolved in tung oilon heating, but exhibited a strong phenolic odor. This odor was quiteapparent despite the fact that the resin during the heating had lost 210parts in weight.

Example 5.Tlm heat-hardened resin of Example 4 was blown with steam at155 C. for about 2 hours. Complete deodorization resulted. The resinthus obtained was easily dissolved in tung oil on heating together atabout 125 C. The resins of Examples 3 and 4 dissolved in tung oilwhenheated with the oil to a higher temperature, 225 to 230 C. beingsuitable.

Other xylenol-containing fractions of coal tar acids may be used, forexample a fraction boiling between 205 and 220 C. Also the pure xylenolsthemselves may be employed. Thus, sym.-xylenol can be obtained from thecrude xylenol mixture by close fractionation in the neighborhood of 219C., or it can be isolated from higher-boiling xylenol fractions by meansof its sodium salt which is sparingly soluble in water.

Example 6.A crude mixture 91 xylenols was distilled and the fractionboiling between 218 and 223 C. was collected. This was treated withsodium hydroxide solution and the sodium salt which separated was washedand converted to the free xylenol by adding sulphuric acid to a diluteaqueous solution of the salt. parts sym.-xylenol thus obtained, 48 parts37% formaldehyde and 24 parts 30% aqueous ammonia were mixed and heatedto boiling. Water was poured off from the oily layer which separated.Heating the oily material to 118 C. gave a soft resin which dissolved intung oil when the latter was heated to about 200 C. In order todeacridify the resin it may be heated to about 150 C. andsteam-distilled as was done in Example 3.

1,3,4-Xylenol obtained by steam distillation of Example 3 is also anexample of a pure xylenol which may be used in forming resins.

Example 7. parts 1,3,4-xylenol, 67 parts 37% formaldehyde and 1 partsodium hydroxide were mixed and gently warmed. An exothermic reactionoccurred and a light-colored resin separated. The water layer was pouredoff, after 1 which the resin was washed to free it from alkali andheated to 120 C. A hard light-colored resin was obtained.

Example 8.250 parts xylenols distilling between 205 and 220 C. weremixed with 265 parts of a 25% solution of formaldehyde obtained byoxidation of natural gas. The mixture was allowed to stand for 4 daysand was then heated to C. in order to drive off all water. A soft resincontaining some unreacted xylenols was obtained. This was soluble intung oil. The unreacted xylenols may be removed by steam distillationand the resin thereby hardened anddeacridlzed.

Instead of dissolving the xylenol resins in raw.

drying oils I may use boiled or blown oils, or oils otherwiseheat-treated prior to incorporation of the resins. Also, I may dissolvethe resins in raw tung oil and the like and then add a bodied drying oilsuch as boiled perilla oil. One part of the resin of Example 8 wasdissolved in 2 parts tung oil by heating the mixture to 250 0. .Then 3parts bodied linseed oil was added and a clear solution was obtained.

As pointed out above, the phenol aldehyde resins of this invention maybe fused with rosin or rosin ester, or with other natural resins andnatural resin esters. Also they may be fused with, or used inconjunction with, synthetic resins such as are obtained by the action ofaluminum chloride on distillates of the vapor-phase cracking ofpetroleum. (See for example U. S. Patent No. 1,836,629). Such petroleumresins usedalone give very rapid drying varnishes; however, thesevarnishes possess certain defects. An insoluble precipitate may formwhen they are thinned and this must be removed by filtration ordecantation in order to get a clear, marketable product. varnishesskin-over rapidly when stored. Also there is a tendency for tung oilvarnishes to form opaque, frosted films during drying unless a very hightemperature is used in their preparation. A mixture of a phenol resinsuch as Example 3 and petroleum resin in suitable proportions yields avarnish which has none of the defects such as are present when thepetroleum resin is used alone. Thus, addition of 10 per cent of theresin of Example 3 to the petroleum resin prevents frosting of a tungoil varnish made from the mixture, and reduces the skinning-overtendency. 1 I part xylenol resin to 2 parts petroleum resin The forins avarnish which shows only slight sedimentation. Mixtures of petroleumresin and xylenol resin form varnishes which dry faster than whenxylenol resin is used alone.

The petroleum resin as described above also may be used with phenolresins which ordinarily are of low oil-solubility. Thus, a mixture ofpetroleum resin and phenol or cresol resin may be used to form avarnish.

Example 9.100 parts m-p-cresol and 56 parts 37% formaldehyde solutionwere heated under a reflux condenser for 5 hours. Water was thendistilled off and the resin heated to 200 C. for 5 minutes. A hardbrittle resin was obtained which was only slightly soluble in dryingoils. Equal parts of the cresol and petroleum resin were heated to 240C. A turbid melt formed at first and heating at 240 C. Was continueduntil the fused mass was practically clear. The composite resin thusobtained was soluble in tung oil. It may be steam-distilled if desiredin order to deacridify it. The two components of the composite resinalso may be dissolved in tung oil without preliminary fusion of themixture.

The following examples are given in order to indicate more fully theconditions involved in the process of de-acridifying resins according tothis invention.

Example 10.-l lbs. xylenols (210225 C. fraction) and lbs. 37%formaldehyde were heated under a reflux condenser for 2 hours. Water wasthen distilled from the mixture and the temperature was taken to 150 C.during 3hours. "Then steam was passed through the fused resin. Within ashort time after introduction of steam the mass became viscous andshowed signs of gelatinization. Steam was shut off and by carefulheating, as not to overheat the resin locally and cause discoloration,the resin was converted to a freely mobile condition at about 180 C.This was then steam-distilled for 5 hours and the product wassubstantially free from odor and soluble in tung oil.

Example 11.Another batch of resin was made using the same quantities ofmaterials as in Example 10, but the temperature of the reaction mixturewas increased more rapidly after removal of the water; and steam was notintroduced until the temperature of the resin had reached 180 C.Thus,after distillation of water, the temperature was raised to, 180 C.during 3 hours'and steam was then passed in. The resin remained in afluid condition and after steam distilling for 6 hours the product wascompletely de-acridified.

If steam-treatment of the resin in Example 10 is continued aftergelatinization has started, an

infusible product is likely to be obtained. This may be converted into afusible oil-soluble resin by fluxing with xylenol.

Example 12.-The reaction of Example 10 was carried out and the resinheated to 150 C. after distilling off the water, as indicated. Steam wasthen passed into the mass for one-half hour. An infusible gel wasobtained. This was converted to a fusible resin as follows: 1 lb.xylenols (2l0-225 C. fraction) was heated to 180 C. and 7 lbs. of thegelatinized resin was added gradually over a period of 4 hours, keepingthe temperature at about 180 C. After all the gel had been introducedthe mixture was heated 3 hours longer and a mobile solution of resin ina lesser proportion of xylenol was obtained. Steam distillation as inExample 11 served to remove excess xylenols and resulted in a fusible,hard," brittle, oil-soluble resin.

In the process of steam-distillation in order to deacridify anoil-soluble phenolic resin, another advantage lies in the fact that alight colored resin is obtained even when moderately dark-coloredxylenols are involved. This is ex-. plainable on the ground that air,with, concommitant oxidation, is excluded during a large part of thetime the resin is heated, and also that certain color-producing bodiesare volatilized or decomposed during the distillation. In one case.xylenols of straw color'were used; in another case, freshly distilledalmost water-white xylenols. The resins obtained from these twomaterials were pale yellow, oil-soluble resins of practically the samecolor.

In this manner a de-acridified, de-xylenated oil-soluble phenol-aldehyderesin is obtained. The step ofheating a xylenol formaldehyde resincontaining free xylenolfor a sufiicient period serves to make itgel-resistant on de-xylenating, whereupon the free xylenol may beremoved by distillation at atmospheric pressure or at pressures above orbelowatmospheric or by blowing with steam either at atmospheric pressureor at pressures above or below atmospheric. It may be noted that theterm de-acridifying involves the step of removing not only free xylenolbut any accompanying nitrogenous or other bodies of acrid odor.

What I claim is:

1. A solution of a reaction product ofa ketone, xylenol, and an aldehydein a drying oil.

2. A solution of a reaction product of acetone, xylenol and an aldehydein a drying oil.

3. A solution of a reaction product of acetone, xylenol and acetaldehydein a drying oil.

4. A- solution of a reaction product of acetone, xylenol andformaldehyde in a drying oil.

CARLETON ELLIS.

